Fungicidal agents

ABSTRACT

A synergistic fungicidal composition comprising a fungicidally effective amount of at least one amino compound of the formula ##STR1## in which R represents optionally substituted, cycloalkyl or optionally substituted aryl, 
     R 1  represents hydrogen or alkyl, 
     R 2  represents alkyl, 
     R 3  represents alkyl and 
     R 4  represents alkyl, alkenyl or alkinyl, or 
     R 3  and R 4 , together with the nitrogen atom to which they are bonded, represent an optionally substituted saturated heterocyclic radical, which can contain further hetero-atoms, 
     X represents oxygen or sulphur, 
     Y represents oxygen, sulphur or the methylene group, 
     m represents 0 or 1 and 
     n represents 0 or 1, 
     or an addition product thereof with an acid, metal salt or quaternizing agent, and at least one member selected from the group consisting of several individually known fungicides.

The invention relates to new fungicidal synergistic active compoundcombinations of particular amino compounds, some of which are known, andother known fungicidal active compounds.

It is already known that certain amino compounds, such as, for example,the amino-ketals4-(3,5-dimethylpiperidin-1-yl-methyl)-2-[1-(4-fluorophenyl)-2-methyl-prop-2-yl]-2-methyl-1,3-dioxolaneor2-[1-(4-fluorophenyl)-2-methyl-prop-2-yl]-2-methyl-4-(3-methyl-piperidin-1-yl-methyl)-1,3-dioxolane,have fungicidal properties (compare, for example, DE-OS (GermanPublished Specification) 3,305,769).

The following groups of fungicidal active compounds are also known:

(A) Azoles, such as, for example,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one(compare, for example, R. Wegler "Chemie der Pflanzenschutz- undSchadlingsbekampfungsmittel" ("Chemistry of Plant Protection Agents andAgents for combating pests"), Volume 4, pages 206 to 208, SpringerVerlag, Berlin, Heidelberg, New York 1977),

(B) Pyrimidine derivatives, such as, for example,(2,4-dichlorophenyl)-(phenyl)-pyrimidin-5-yl)-carbinol or(2-chlorophenyl)-(4-chlorophenyl)-(pyrimidin-5-yl)-carbinol (compare,for example, R. Wegler "Chemie der Pflanzenschutz- andSchadlingsbekampfungsmittel" ("Chemistry of Plant Protection Agents andAgents for combating pests"), Volume 4, pages 213/214; Springer VerlagBerlin, Heidelberg, New York 1977),

(C) Pyridine derivatives, such as, for example, S-(n-butyl)S-(4-t-butyl-phenylmethyl) N-(3-pyridyl)-iminodithiocarbonate (compare,for example, Japanese Patent Application Ja 43,334/72), and

(D) Morpholino compounds, such as, for example,cis-2,6-dimethyl-4-[3-(4-t-butylphenyl)-2-methyl-prop-1-yl]morpholine(compare, for example, DE-OS (German Published Specification)2,656,747).

Synergistic mixtures of azoles and other fungicides which have aconsiderably higher action than that expected from the actions of theindividual components are also known (compare, for example, DE-OS(German Published Specification) 2,552,967 corresponding to U.S. Pat.No. 31693).

The activity of the known fungicidal active compounds as individualcompounds and also that of the known synergistic active compoundcombinations are, however, not always completely satisfactory in allfields of application, especially when low amounts and concentrationsare used.

It has now been found, surprisingly, that the new active compoundcombinations of particular amino compounds, some of which are known, ofthe formula (I) ##STR2## in which R represents optionally substitutedcycloalkyl or optionally substituted aryl,

R¹ represents hydrogen or alkyl,

R² represents alkyl,

R³ represents alkyl and

R⁴ represents alkyl, alkenyl or alkinyl, or

R³ and R⁴, together with the nitrogen atom to which they are bonded,represent an optionally substituted saturated heterocyclic radical,which can contain further hetero-atoms,

X represents oxygen or sulphur,

Y represents oxygen, sulphur or the methylene group,

m represents 0 or 1 and

n represents 0 or 1,

or acid addition salts, metal salt complexes or quaternization productsthereof which are tolerated by plants, on the one hand, and, on theother hand, known fungicidal active compounds either from the group (A₁)with the formula (IIa) ##STR3## in which R⁵ represents alkyl, alkenyl,alkinyl, cycloalkyl, alkylcarbonyl, optionally substituted phenyl,optionally substituted phenylcarbonyl, an optionally substitutedheterocyclic radical, the cyano group, an ester grouping or an acidamide radical,

R⁶ represents alkyl, cycloalkyl or optionally substituted phenyl,

R⁷ represents optionally substituted phenyl and

Z represents nitrogen or the CH group,

or acid addition salts or metal salt complexes thereof which aretolerated by plants, and/or from the group (A₂) with the formula (IIb)##STR4## in which R⁸ represents hydrogen or in each case optionallysubstituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl, aryloxy orheteroaryloxy,

R⁹ represents in each case optionally substituted alkylcarbonyl orarylcarbonyl, or represents a functional derivative of these groups,such as oxime, hydrazone or ketal, or furthermore represents a carboxylgroup or a functional derivative thereof, such as ester or amide, orfurthermore represents a radical ##STR5## or a functional derivativethereof, such as ester or ether, wherein

R¹⁰ represents in each case optionally substituted alkyl or aryl, and

Z has the abovementioned meaning,

or acid addition salts or metal salt complexes thereof which aretolerated by plants, and/or from the group (A₃) with the formula (IIc)##STR6## in which R¹¹ represents in each case optionally substitutedaryl or aryloxy and

R¹² represents alkyl or a radical --S(O)_(p) --R⁸,

wherein

p represents 0, 1 or 2 and

R⁸ has the abovementioned meaning, or

R¹² also represents in each case optionally substituted alkylcarbonyl orarylcarbonyl or a functional derivative of these groups, such as oxime,hydrazone or ketal, or represents a radical ##STR7## or a functionalderivative thereof, such as ester or ether, wherein

R¹⁰ and Z have the abovementioned meaning,

or acid addition salts or metal salt complexes thereof which aretolerated by plants, and/or from the group (A₄) with the formula (IId)##STR8## in which R¹³ represents in each case optionally substitutedalkyl, alkenyl, alkinyl, cycloalkyl, heterocyclyl, aryl or heteroaryl,

R¹⁴ represents in each case optionally substituted alkyl, alkenyl,alkinyl, cycloalkyl or aryl,

R¹⁵ represents chlorine, cyano or a radical --OR¹⁶,

wherein

R¹⁶ represents hydrogen or in each case optionallyl substituted alkyl,alkenyl, alkinyl or acyl, and

Z has the abovementioned meaning,

or acid addition salts or metal salt complexes thereof which aretolerated by plants, and/or from the group (A₅) with the formula (IIe)##STR9## in which R¹⁸ represents in each case optionally substitutedalkyl, cycloalkyl or aryl,

R¹⁹ represents in each case optionally substituted alkylcarbonyl orarylcarbonyl or a functional derivative of these groups, such as oxime,hydrazone or ketal, or represents a radical ##STR10## or a functionalderivative thereof, such as ester or ether, wherein

R¹⁰ and Z have the abovementioned meaning, or acid addition salts ormetal salt complexes thereof which are tolerated by plants, and/or fromthe group (A₆) with the formula (IIf) ##STR11## in which R²⁰ representsalkyl, optionally substituted phenyl or optionally substituted phenoxy,

R²¹ represents in each case optionally substituted alkylcarbonyl orarylcarbonyl or a functional derivative of these groups, such as oxime,hydrazone or ketal, or represents a radical ##STR12## or a functionalderivative thereof, such as ester, ether or trialkylsilyl ether,

R²² represents hydrogen or in each case optionally substituted aryl oraryloxy and

R¹⁰ and Z have the abovementioned meaning,

or acid addition salts or metal salt complexes thereof which aretolerated by plants, and/or from the group (A₇) with the formula (IIg)##STR13## in which R²³ represents alkyl,

R²⁴ represents in each case optionally substituted alkyl, alkenyl,alkinyl, cycloalkyl or aryl,

A represents oxygen or sulphur and

Z has the abovementioned meaning,

or acid addition salts or metal salt complexes thereof which aretolerated by plants, and/or from the group (A₈) with the formula (IIh)##STR14## in which R²⁵ represents optionally substituted aryl,

R²⁶ and R²⁷ in each case independently of one another representhydrogen, alkyl or aryl, or together represent a divalent alkyleneradical,

R²⁸ represents hydrogen or akyl and

Z has the abovementioned meaning,

or acid addition salts or metal salt complexes thereof which aretolerated by plants, and/or from the group (B) with the formula (III)##STR15## in which R²⁹ represents alkyl, cycloalkyl or optionallysubstituted aryl and

R³⁰ represents in each case optionally substituted aryl, aralkyl oraryloxyalkyl,

or acid addition salts thereof which are tolerated by plants, and/orfrom the group (C) with the formula (IV) ##STR16## in which R³¹ and R³²independently of one another represent alkyl or optionally substitutedaralkyl,

or acid addition salts thereof which are tolerated by plants, and/orfrom the group (D) with the formula (V) ##STR17## in which R³³represents alkyl, cycloalkyl or halogenoalkyl,

R³⁴ and R³⁵ independently of one another represent hydrogen, alkyl,hydroxyalkyl, hydroxyl or aryl,

E represents oxygen, sulphur, divalent alkylene or the >N--R³⁶ group,

wherein

R³⁶ represents hydrogen or alkyl, and

a represents 0 or 1,

or acid addition salts thereof which are tolerated by plants--all thegeometric and optical isomers of the compounds of the formulae (I) to(V) being included-have a particularly high fungicidal activity.

Surprisingly, the fungicidal action of the active compound combinationsaccording to the invention of the amino compounds, some of which areknown, of the formula (I), on the one hand, and azole derivatives of theformulae (IIa-h) and/or pyrimidine derivatives of the formula (III)and/or pyridine derivatives of the formula (IV) and/or amino compoundsof the formula (V), on the other hand, is higher than the action of theindividual components and also higher than the sum of the actions of theindividual components (synergistic effect).

The active compound combinations according to the invention thusrepresent an enrichment of the art.

Formula (I) provides a general definition of the particular aminocompounds, some of which are known, which are to be used for the activecompound combinations according to the invention. Preferred compounds ofthe formula (I) are those in which

R represents phenyl or cyclohexyl which is optionally monosubstituted orpolysubstituted by identical or different substituents, possiblesubstituents being: halogen and in each case straight-chain or branchedalkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy orhalogenoalkylthio with in each case 1 to 4 carbon atoms and, whereappropriate, 1 to 9 identical or different halogen atoms,

R¹ represents hydrogen or straight-chain or branched alkyl with 1 to 4carbon atoms,

R² represents straight-chain or branched alkyl with 1 to 4 carbon atoms,

R³ represents straight-chain or branched alkyl with 1 to 6 carbon atomsand

R⁴ represents in each case straight-chain or branched alkyl, alkenyl oralkinyl with in each case up to 8 carbon atoms, or

R³ and R⁴, together with the nitrogen atom to which they are bonded,represent a saturated heterocyclic radical which has 5 to 7 ring membersand 1 or 2 hetero-atoms and is optionally monosubstituted orpolysubstituted by identical or different substituents, possiblehetero-atoms being nitrogen and oxygen and possible substituents being:straight-chain or branched alkyl with 1 to 4 carbon atoms, hydroxymethyland derivatives thereof, such as ethers and esters, and straight-chainor branched alkoxycarbonyl with 1 to 4 carbon atoms,

X represents oxygen or sulphur,

Y represents oxygen, sulphur or the methylene group,

m represents 0 or 1 and

n represents 0 or 1,

and acid addition salts, metal salt complexes and quaternizationproducts thereof which are tolerated by plants.

Particularly preferred components of the mixture are amino compounds ofthe formula (I) in which

R represents phenyl which is optionally mono-, di- or tri-substituted byidentical or different substituents, possible substituents being:fluorine, chlorine, bromine, methyl, ethyl, n- and i-propyl, n-, i-, s-and t-butyl, methoxy, ethoxy, n- and i-propoxy, methylthio,trifluoromethyl, trifluoromethoxy and trifluoromethylthio, or representscyclohexyl which is optionally mono-, di-, tri-, tetra- orpenta-substituted by identical or different substituents, possiblesubstituents being: methyl, ethyl and n- or i-propyl,

R¹ represents hydrogen or methyl,

R² represents methyl or ethyl,

R³ represents methyl and

R⁴ represents methyl, ethyl, n- or i-propyl, n- or i-butyl, n- ori-pentyl, n- or i-hexyl, allyl, butenyl, n- or i-pentenyl, n- ori-hexenyl, propargyl, butinyl, n- or i-pentinyl or n- or i-hexinyl, or

R³ and R⁴, together with the nitrogen atom to which they are bonded,represent a heterocyclic radical of the formula ##STR18## which isoptionally mono-, di-, tri- or tetrasubstituted by identical ordifferent substitutents, possible substituents being: methyl, ethyl,phenyl, hydroxymethyl, methoxymethyl, ethoxymethyl, acyloxymethyl,methoxycarbonyl or ethoxycarbonyl,

X represents oxygen or sulphur,

Y represents oxygen, sulphur or the methylene group,

m represents 0 or 1 and

n represents 0 or 1,

and acid addition salts, metal salt complexes and quaternizationproducts thereof which are tolerated by plants.

Some of the compounds of the formula (I) are disclosed in EuropeanPatent Application 97,822. Others are disclosed in German PatentApplication 33 28 151 corresponding to U.S. Application Ser. No. 630,487filed July 13, 1984, now pending, German Patent Application 33 24 769corresponding to U.S. Application Ser. No. 624,889 filed June 27, 1984,now pending, and German Patent Application 34 14 996.

They are obtained, for example, by a process in which compounds of theformula (VI) ##STR19## in which R, R¹, R², X, Y, m and n have theabovementioned meaning and

A represents an electron-withdrawing leaving group, in particularchlorine or bromine, methanesulphonyloxy or p-toluenesulphonyloxy,

are reacted with amines of the formula (VII) ##STR20## to which R³ andR⁴ have the abovementioned meaning,

if appropriate in the presence of a diluent, such as, for example,ethanol, if appropriate in the presence of an acid-binding agent, suchas, for example, potassium carbonate, and if appropriate in the presenceof a catalyst, such as, for example, potassium iodide, at temperaturesbetween 50° C. and 250° C.

The following acids can preferably be used to prepare acid additionsalts of the compounds of the formula (I) which are tolerated by plants:hydrogen halide acids, such as, for example, hydrochloric acid andhydrobromic acid, in particular hydrochloric acid, and furthermorephosphoric acid, nitric acid, sulphuric acid, mono-, bi- andtri-functional carboxylic acids and hydroxycarboxylic acids, such as,for example, acetic acid, maleic acid, succinic acid, fumaric acid,tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid,and sulphonic acids, such as, for example, p-toluenesusphonic acid and1,5-naphthalenedisulphonic acid.

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, suchas, for example, by dissolving a compound of the formula (I) in asuitable inert solvent and adding the acid, such as, for example,hydrochloric acid, and they can be isolated in a known manner, forexample by filtration, and, if appropriate, purified by washing with aninert organic solvent.

Salts of metals of main groups II to IV and of sub-groups I and II andIV to VIII can preferably be used to prepare metal salt complexes of thecompounds of the formula (I), examples of metals which may be mentionedbeing copper, zinc, manganese, magnesium, tin, iron and nickel.

Possible anions of salts are those which, preferably, are derived fromthe following acids: hydrogen halide acids, such as, for example,hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid,nitric acid and sulphuric acid.

The metal salt complexes of compounds of the formula (I) can be obtainedin a simple manner by customary processes, thus, for example, bydissolving the metal salt in alcohol, for example ethanol, and addingthe solution to the compound of the formula (I). The metal saltcomplexes can be purified in a known manner, for example by filtration,isolation and, if appropriate, by recrystallization.

Alkyl or aralkyl halides, sulphates or sulphonates, such as, forexample, methyl iodide, dimethyl or diethyl sulphate, benzyl chloride orbromide or methyl or ethyl p-toluenesulphonate, can preferably be usedto prepare quaternization products of the compounds of the formula (I).

The quaternization products of the compounds of the formula (I) can beobtained in a simple manner by customary methods, such as, for example,by reacting the reaction components in a suitable solvent, such as, forexample, acetonitrile or acetone, and they can be isolated in a knownmanner, for example by precipitation with a suitable precipitatingagent, such as, for example, diethyl ether, and filtration with suction,and purified by washing with an inert organic solvent.

The fungicides of group A₁ to A₈, B, C and D to be used as components inthe mixture are already described in the literature; in this context,compare the following data:

(A₁) Compounds of the formula (IIa): DE-OS (German PublishedSpecification) 1,670,976; German Patent Specification 1,795,249; DE-OS(German Published Specification) 2,128,700 and DE-OS (German PublishedSpecification) 2,628,152.

(A₂) Compounds of the formula (IIb): DE-OS (German PublishedSpecification) 2,063,857; DE-OS (German Published Specification)2,105,490; DE-OS (German Published Specification) 2,201,063; DE-OS(German Published Specification) 2,324,010; DE-OS (German PublishedSpecification) 2,325,156; DE-OS (German Published Specification)2,333,354; DE-OS (German Published Specification) 2,431,407; DE-OS(German Published Specification) 2,547,953; DE-OS (German PublishedSpecification) 2,551,560; DE-OS (German Published Specification)2,600,799; DE-OS (German Published Specification) 2,610,022; DE-OS(German Published Specification) 2,632,603; DE-OS (German PublishedSpecification) 2,635,663; DE-OS (German Published Specification)2,638,470; DE-OS (German Published Specification) 2,640,823; DE-OS(German Published Specification) 2,654,890; DE-OS (German PublishedSpecification) 2,720,654; DE-OS (German Published Specification)2,720,949; DE-OS (German Published Specification) 2,734,365; DE-OS(German Published Specification) 2,734,426; DE-OS (German PublishedSpecification) 2,737,489; DE-OS (German Published Specification)2,756,269; DE-OS (German Published Specification) 2,800,544; DE-OS(German Published Specification) 2,811,919; DE-OS (German PublishedSpecification) 2,819,879; DE-OS (German Published Specification)2,832,233; DE-OS (German Published Specification) 2,832,234; DE-OS(German Published Specification) 2,918,467; DE-OS (German PublishedSpecification) 2,926,096; DE-OS (German Published Specification)2,943,631; DE-OS (German Published Specification) 2,951,163; DE-OS(German Published Specification) 2,951,164; DE-OS (German PublishedSpecification) 3,002,430; DE-OS (German Published Specification)3,019,049; DE-OS (German Published Specification) 3,048,266; DE-OS(German Published Specification) 3,048,267; DE-OS (German PublishedSpecification) 3,139,370; DE-OS (German Published Specification)3,209,431; DE-OS (German Published Specification) 3,208,194; DE-OS(German Published Specification) 3,310,830; European PublishedApplication 15,639; European Published Application 60,962 and U.S.Patent Specification 4,166,854.

(A₃) Compounds of the formula (IIc): DE-OS (German PublishedSpecification) 2,306,495; DE-OS (German Published Specification)2,335,020; DE-OS (German Published Specification) 2,350,122; DE-OS(German Published Specification) 2,063,857; DE-OS (German PublishedSpecification) 2,735,872 and DE-OS (German Published Specification)2,645,496.

(A₄) Compounds of the formula (IId): DE-OS (German PublishedSpecification) 2,604,047; DE-OS (German Published Specification)2,736,122; DE-OS (German Published Specification) 2,920,374; DE-OS(German Published Specification) 3,018,866; DE-OS (German PublishedSpecification) 3,106,076; DE-OS (German Published Specification)3,202,601; DE-OS (German Published Specification) 3,237,400; DE-OS(German Published Specification) 3,242,222; DE-OS (German PublishedSpecification) 3,242,252; DE-OS (German Published Specification)3,245,504; DE-OS (German Published Specification) 3,307,216; EuropeanPublished Application 15,756; European Published Application 36,153;European Published Application 44,605; European Published Application46,337; European Published Application 47,594; European PublishedApplication 48,548; European Published Application 52,424; EuropeanPublished Application 54,974; European Published Application 55,997;European Published Application 61,835; European Published Application78,594; European Published Application 91,309; European PublishedApplication 97,469, European Published Application 97,480 and EuropeanPublished Application 101,212.

(A₅) Compounds of the formula (IIe): DE-OS (German PublishedSpecification) 2,645,617; DE-OS (German Published Specification)2,838,847; DE-OS (German Published Specification) 2,906,061; DE-OS(German Published Specification) 2,929,602; DE-OS (German PublishedSpecification) 2,938,422; DE-OS (German Published Specification)3,010,560; DE-OS (German Published Specification) 3,025,242 and DE-OS(German Published Specification) 3,028,330.

(A₆) Compounds of the formula (IIf): DE-OS (German PublishedSpecification) 2,845,980; DE-OS (German Published Specification)2,928,967; DE-OS (German Published Specification) 2,931,755 and EuropeanPublished Application 28,363.

(A₇) Compounds of the formula (IIg): DE-OS (German PublishedSpecification) 2,429,523; DE-OS (German Published Specification)2,856,974 and U.S. Patent Specification 4,208,411.

(A₈) Compounds of the formula (IIh): European Published Application94,167.

(B) Compounds of the formula (III): DE-OS (German PublishedSpecification) 1,770,288 and DE-OS (German Published Specification)2,742,173.

(C) Compounds of the formula (IV): Japanese Patent Application43,334,172

(D) Compounds of the formula (V): DE-OS (German Published Specification)2,830,127.

Particularly preferred partners in the mixtures are: ##STR21##

The weight ratios of the groups of active compound in the activecompound combinations can vary within relatively wide limits. Ingeneral, 0.01 to 50 parts by weight of active compound from activecompound classes (A) to (D), preferably 0.02 to 20 parts by weight, andparticularly preferably 0.5 to 5 parts by weight of the last group, arepresent per part by weight of compound of the formula (I).

The active compound combinations according to the invention exhibit apowerful microbicidal action and can be employed in practice forcombating undesired micro-organisms. The active compound combinationsare suitable for use as plant protection agents, above all asfungicides.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

The good toleration, by plants, of the active compound combinations, atthe concentrations required for combating plant diseases, permitstreatment of above-ground parts of plants, of vegetative propagationstock and seeds, and of the soil.

The active compound combinations according to the invention have a verybroad action spectrum and can be used against parasitic fungi whichinfect the above-ground parts of plants or attack the plants from thesoil, as well as seed-borne pathogens. Such active compound combinationsare of particular practical importance as seed dressing agents againstphytopathogenic fungi which are transmitted with the seed or occur inthe soil and attack the crop plants from there. These are seedlingdiseases, root rot and stalk, stem, leaf, blossom, fruit and seeddiseases, which are caused, in particular, by species of Tilletia,Urocystis, Ustilago, Septoria, Typhula, Rhynchosporium,Helminthosphorium and Fusarium. Due to the systemic action of one of thepartners in the mixture, the plants are also frequently still protectedfor a very long time after the dressing from pathogens which can attackvarious parts of the shoot, for example Erysiphe graminis and species ofPuccinia. The active compound combinations can also be used as soiltreatment agents against phytopathogenic fungi, and have an actionagainst root rot and tracheomycoses, which are caused, for example, bypathogens of the genus Pythium, Verticillium, Phialophora, Rhizoctonia,Fusarium and Thielaviopsis.

However, the active compound combinations according to the inventionalso exhibit an outstanding action, when applied directly to theabove-ground parts of plants, against pathogens on various crop plants,such as powdery mildew fungi (Erysiphe, Uncinula, Sphaerotheca andPodosphaera species and Leveillula taurica), rust fungi, Venturiaspecies, Cercospora species, Alternaria species, Botrytis species,Phytophthora species, Peronospora species, Pyricularia oryzae,Pellicularia sasakii, Fusarium species, Pyrenophora species,Cochliobolus species, Septoria species and Pseudocercosporellaherpotrichoides.

When applied in appropriate amounts, the active compound combinationsaccording to the invention also exhibit an insecticidal, acaricidal,insect development-inhibiting, bactericidal and plant growth-regulatingaction.

The active compound combinations can be converted to the customaryformulations, such as solutions, emulsions, wettable powders,suspensions, powders, dusts, foams, pastes, soluble powders, granules,aerosols, suspension-emulsion concentrates, seed treatment powders,natural and synthetic materials impregnated with active compound, veryfine capsules in polymeric substances and in coating compositions forseed, and formulations used with burning equipment, such as fumigatingcartridges, fumigating cans, fumigating coils and the like, as well asULV cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as cnlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons such as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks; as emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compound combinations according to the invention can bepresent in the formulations or in the various use forms as a mixturewith other known active compounds, such as fungicides, bactericides,insecticides, acaricides, nematicides, herbicides, bird repellents,growth factors, plant nutrients and agents for improving soil structure.

The active compound combinations can be used as such or in the form oftheir formulations or the use forms prepared therefrom by furtherdilution, such as ready-to-use solutions, emulsions, suspensions,powders, pastes and granules. They are used in the customary manner, forexample by watering, immersion, spraying, atomizing, misting,vaporizing, injecting, forming a slurry, brushing on, dusting,scattering, dry dressing, moist dressing, wet dressing, slurry dressingor encrusting.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

The following use examples serve for illustration.

In order to demonstrate synergism between the active compounds used inthe following experiments, the results were evaluated by the methoddescribed by R. S. Colby (Calculating Synergistic and AntagonisticResponses of Herbicides Combinations; Weeds 15, 20-22, 1967). Theexpected infestation in % of the untreated control was calculatedaccording to the equation

    E=(X·Y)/100

In this equation, X and Y denote the disease infestation-expressed in %of the untreated control-which the two products allow when usedseparately. A synergistic effect exists if the fungicidal action of theactive compound combination is greater than that of the active compoundsapplied individually. In this case, the infestation actually observedmust be less than the value of the expected infestation (E) calculatedfrom the above-mentioned formula.

EXAMPLE A Pyrenophora teres test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofPyrenophora teres. The plants then remain in an incubation cabinet at20° C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

                                      TABLE A                                     __________________________________________________________________________    Pyrenophora teres test (barley)/protective                                                                 Active compound  Disease                                                      concentration    infestation                                                  in the spray     in % of the                                                  liquor in %      untreated                       Active compound              by weight        control                         __________________________________________________________________________     ##STR22##                   0.005            25.0                            (known) (IIb-2)                                                                ##STR23##                   0.005            57.5                            (known) (I-111)                                                                ##STR24##                   0.005            42.5                            (known) (I-92)                                                                 ##STR25##                   0.005            50.0                            (known) (I-87)                                                                __________________________________________________________________________                                 observed expected                                __________________________________________________________________________                                 Infestation                                                                            Infestation (E)                                                      after using                                                                            after using                                                          the mixture                                                                            the mixture                                                          in % of the untreated control                    Mixture                                                                       (IIb-2) + (I-111) = 1:1 0.005 + 0.005                                                                      0.0      14.4                                    (IIb-2) + (I-92) = 1:1 0.005 + 0.005                                                                       0.0      10.6                                    (IIb-2) + (I-87) = 1:1 0.005 + 0.005                                                                       0.0      12.5                                    __________________________________________________________________________

EXAMPLE B Venturia test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabinet at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

                                      TABLE B                                     __________________________________________________________________________    Venturia test (apple)/protective                                                                            Infestation in % at an                                                        active compound                                                               concentration of                                Active compound               0.5 ppm                                         __________________________________________________________________________     ##STR26##                    74                                              (known) (IIb-3)                                                                ##STR27##                    81                                              (known) (I-140)                                                                ##STR28##                    74                                              (known) (I-89)                                                                Mixture:                      35                                              (IIb-3) + (I-140) = 1:1 (0.5 ppm + 0.5 ppm)                                   Mixture:                      18                                              (IIb-3) + (I-89) = 1:1 (0.5 ppm + 0.5 ppm)                                    __________________________________________________________________________

PREPARATION EXAMPLES Example (I-1) ##STR29##

30.3 g (0.1 mole) of4-chloromethyl-2-[1-(4-chlorophenyl)-2-methyl-prop-2-yl]-2-methyl-1,3-dioxolane,23 g (0.2 mole) of 3-hydroxymethylpiperidine and 0.1 g of potassiumiodide in 100 ml of ethanol are heated at 150° C. under pressure (2 bar)for 15 hours. For working up, the solvent is removed in vacuo, theresidue is taken up in 100 ml of methylene chloride, the mixture iswashed twice with 100 ml of water each time and dried over sodiumsulphate and the solvent is removed again in vacuo.

38 g (100% of theory) of2-[1-(4-(chlorophenyl)-2-methyl-prop-2-yl]-4-[(3-hydroxymethylpiperidin-1-yl)-2-methyl]-1,3-dioxolaneof refractive index n²⁰ =1.5226 are obtained.

Example (I-2) ##STR30##

2.4 g (0.0181 mole) of furan-2-carboxylic acid chloride are added to 6.9g (0.018 mole) of2-[1-(4-chlorophenyl)-2-methyl-prop-2-yl]-4-[(3-hydroxymethylpiperidin-1-yl)-methyl]-2-methyl-1,3-dioxolanein 70 ml of methylene chloride at room temperature, with stirring, andthe mixture is stirred for a further 2 hours. For working up, 50 ml ofsaturated sodium bicarbonate solution are added, the organic phase isseparated off, the aqueous phase is extracted twice with 50 ml ofmethylene chloride each time, the combined methylene chloride phases aredried over sodium sulphate and the solvent is removed in vacuo.

6 g (70% of theory) of2-[1-(4-chlorophenyl)-2-methyl-prop-2-yl]-4-(furyl-2-carbonyloxymethyl)-piperidin-1-yl-methyl]-2-methyl-1,3-dioxolaneare obtained as an oil.

¹ H-NMR (CDCl₃): δ=4.17 ppm (d, 2H) corresponds to the ##STR31## group.

Preparation of the starting substance ##STR32##

60 g (0.285 mole) of 4-(4-chlorophenyl)-3,3-dimethylbutan-2-one, 63 g(0.57 mole) of 3-chloropropane-1,2-diol and 5.4 g (0.0285 mole) ofp-toluenesulphonic acid are heated in a mixture of 500 ml of toluene and100 ml of n-butanol under reflux for 15 hours, using a water separator.The solvent is then distilled off under a waterpump vacuum and theresidue is subjected to fine distillation under a high vacuum.

After distilling twice, 69 g (80% of theory) of4-chloromethyl-2-[1-(4-chlorophenyl)-2-methyl-prop-2-yl]-methyl-1,3-dioxolaneof boiling point 155° C. under 0.267 mbar are obtained as a cis/transmixture.

The following compounds of the general formula (Ia) in which Y informula (I) represents oxygen are obtained in a corresponding manner andin accordance with the general preparation instructions:

    __________________________________________________________________________     ##STR33##                                                                     Example No.                                                                          ##STR34##                                                                                      ##STR35##   Boiling point: °C./mbar][Refra                                        ctive index: n.sub.D.sup.20Physical                                           constant                                  __________________________________________________________________________    (I-3)                                                                                 ##STR36##                                                                                      ##STR37##  1.5173                                    (I-4)                                                                                 ##STR38##                                                                                      ##STR39##  1.5123                                    (I-5)                                                                                 ##STR40##                                                                                      ##STR41##  1.5269                                    (I-6)                                                                                 ##STR42##                                                                                      ##STR43##  1.5308                                    (I-7)                                                                                 ##STR44##                                                                                      ##STR45##  1.5361                                    (I-8)                                                                                 ##STR46##                                                                                      ##STR47##  1.5362                                    (I-9)                                                                                 ##STR48##                                                                                      ##STR49##  1.5249                                    (I-10)                                                                                ##STR50##                                                                                      ##STR51##  1.5196                                    (I-11)                                                                                ##STR52##                                                                                      ##STR53##  1.5114                                    (I-12)                                                                                ##STR54##                                                                                      ##STR55##  Oil                                       (I-13)                                                                                ##STR56##                                                                                      ##STR57##  1.5041                                    (I-14)                                                                                ##STR58##                                                                                      ##STR59##  1.5112                                    (I-15)                                                                                ##STR60##                                                                                      ##STR61##  1.5273                                    (I-16)                                                                                ##STR62##                                                                                      ##STR63##  250/0.1                                   (I-17)                                                                                ##STR64##                                                                                      ##STR65##  250/0.1                                   (I-18)                                                                                ##STR66##                                                                                      ##STR67##  200/0.1                                   (I-19)                                                                                ##STR68##                                                                                      ##STR69##  250/0.1                                   (I-20)                                                                                ##STR70##                                                                                      ##STR71##  200/0.1                                   (I-21)                                                                                ##STR72##                                                                                      ##STR73##  Oil                                       (I-22)                                                                                ##STR74##                                                                                      ##STR75##  1.4810                                    (I-23)                                                                                ##STR76##                                                                                      ##STR77##  Oil                                       __________________________________________________________________________

Example (I-24) ##STR78##

10 g (0.03 mole) of5-chloromethyl-2-[1-(4-chlorophenoxy)-2-methyl]-prop-2-yl-methyl-1,3-oxathiolaneand 10 g (0.12 mole) of piperidine are heated at 120° C. for 12 hours.After cooling, the reaction mixture is diluted with ethyl acetate,washed twice with water, dried over sodium sulphate and concentrated invacuo. The residue is subjected to bulb tube distillation (boilingpoint: ˜200° C./0.13 mbar) of chromatographed over a silica gel columnwith an eluant mixture of petroleum ether/ethyl acetate=2:1.

8 g (69.5% of theory) of2-[1-(4-chlorophenoxy)-2-methyl]-prop-2-yl-methyl-5-piperidin-1-ylmethyl-1,3-oxathiolaneof refractive index n_(D) ²⁰ =1.5440 are obtained.

The compounds listed below of the general formula (Ib) in which Y informula (I) represents sulphur are obtained in a corresponding mannerand in accordance with the general instructions for the preparation:

    __________________________________________________________________________     ##STR79##                               (Ib)                                  No.Example                                                                         ##STR80##                                                                                     ##STR81##     Melting point °C.index                                                [n.sub.D.sup.20 :]Refractive               __________________________________________________________________________    (I-25)                                                                              ##STR82##                                                                                     ##STR83##    1.5382                                     (I-26)                                                                              ##STR84##                                                                                     ##STR85##    1.5331                                     (I-27)                                                                              ##STR86##                                                                                     ##STR87##    1.5357                                     (I-28)                                                                              ##STR88##                                                                                     ##STR89##    1.5341                                     (I-29)                                                                              ##STR90##                                                                                     ##STR91##    1.5039                                     (I-30)                                                                              ##STR92##                                                                                     ##STR93##    1.5065                                     (I-31)                                                                              ##STR94##                                                                                     ##STR95##    1.5147                                     (I-32)                                                                              ##STR96##                                                                                     ##STR97##    1.5007                                     (I-33)                                                                              ##STR98##                                                                                     ##STR99##    1.5077                                     (I-34)                                                                              ##STR100##                                                                                    ##STR101##   1.5082                                     (I-35)                                                                              ##STR102##                                                                                    ##STR103##   1.5049                                     (I-36)                                                                              ##STR104##                                                                                    ##STR105##   1.5058                                     (I-37)                                                                              ##STR106##                                                                                    ##STR107##   1.5091                                     (I-38)                                                                              ##STR108##                                                                                    ##STR109##   1.5077                                     (I-39)                                                                              ##STR110##                                                                                    ##STR111##   1.5069                                     (I-40)                                                                              ##STR112##                                                                                    ##STR113##   1.5087                                     (I-41)                                                                              ##STR114##                                                                                    ##STR115##   1.5083                                     (I-42)                                                                              ##STR116##                                                                                    ##STR117##   1.5110                                     (I-43)                                                                              ##STR118##                                                                                    ##STR119##   1.5245                                     (I-44)                                                                              ##STR120##                                                                                    ##STR121##   1.5070                                     (I-45)                                                                              ##STR122##                                                                                    ##STR123##   1.5062                                     (I-46)                                                                              ##STR124##                                                                                    ##STR125##   1.5078                                     (I-47)                                                                              ##STR126##                                                                                    ##STR127##   1.5122                                     (I-48)                                                                              ##STR128##                                                                                    ##STR129##   1.5047                                     (I-49)                                                                              ##STR130##                                                                                    ##STR131##   1.5086 (cis form)                          (I-50)                                                                              ##STR132##                                                                                    ##STR133##   1.5039 (cis form)                          (I-51)                                                                              ##STR134##                                                                                    ##STR135##   179-180                                    (I-52)                                                                              ##STR136##                                                                                    ##STR137##   Oil                                        (I-53)                                                                              ##STR138##                                                                                    ##STR139##                                              __________________________________________________________________________

Example (I-54) ##STR140##

16 g (0.044 mole) of2-bromomethyl-5-[1-(4-chlorophenoxy)-2-methyl-prop-2-yl]-5-methyl-tetrahydrofruanare stirred together with 11 g (0.097 mole) ofcis-3,5-dimethylpiperidine at a bath temperature of 140° C. for about 14hours. The resulting reaction mixture is taken up in ether, washedseveral times with water, dried over sodium sulphate and concentrated invacuo. The oily residue is purified by column chromatography (silica gel60/ether-petroleum ether 1:1). 7.8 g (45% of theory) of5-[1-(4-chlorophenoxy)-2-methyl-prop-2-yl]-2-(cis)-(3,5-dimethylpiperidin-1-ylmethyl)-5-methyl-tetrahydrofuranof refractive index n_(D) ²⁰ =1.5049 are obtained.

Preparation of the starting compound ##STR141##

16 g (0.1 mole) of bromine are added dropwise to 28.2 g (0.1 mole) of7-(4-chlorophenoxy)-5-hydroxy-5,6,6-trimethyl-hept-1-ene in 200 ml ofabsolute chloroform at room temperature, with stirring, followed by 13 g(0.1 mole) of quinoline, at -10° C. with cooling. The reaction mixtureis stirred at room temperature for a further 2 hours and concentrated invacuo, the residue is taken up in ether, the mixture is filtered andconcentrated again in vacuo and the residue is stirred at 95° C. on awater-bath for 1 hour. The resulting mixture is taken up in ether andfiltered and the filtrate is washed with 15% strength hydrochloric acidand then with water, dried over sodium sulphate and freed from thesolvent in vacuo. 32.7 g (90% of theory) of2-bromomethyl-5-[1-(4-chlorophenoxy)-2-methylprop-2-yl]-5-methyl-tetrahydrofuranare obtained as an oil, which can be used in the next stage withoutfurther purification. ##STR142##

A solution of 48 g (0.2 mole) of2-[1-(4-chlorophenoxy)-2-methylprop-2-yl]-2-methyl-oxirane in 100 ml ofabsolute tetrahydrofuran is added dropwise to a Grignard solution of 7.2g (0.3 mole) of magnesium and 36 g of allyl bromide in 300 ml ofabsolute ether, while stirring and cooling with ice, and, when theaddition has ended, the mixture is heated at the reflux temperature for4 hours and subsequently stirred at room temperature for 15 hours. Forworking up, the mixture is hydrolysed with aqueous ammonium chloridesolution, the organic phase is separated off and dried over sodiumsulphate, the solvent is removed in vacuo and the residue is distilledunder a high vacuum.

43 g (51% of theory) of7-(4-chlorophenoxy)-5-hydroxy-5,6,6-trimethyl-hept-1-ene of boilingpoint 128° C.-130° C./0.13 mbar are obtained. ##STR143##

70.2 g (0.33 mole) of sodium methylate are added to a suspension of 72 g(0.33 mole) of trimethylsulphoxonium chloride in 71 g (0.3 mole) ofabsolute dimethylsulphoxide in the course of 10 minutes, the mixture isthen diluted with 100 ml of absolute tetrahydrofuran and subsequentlystirred at room temperature for three hours and 68 g (0.3 mole) of1-(4-chlorophenoxy)-2,2-dimethylbutan-3-one in 50 ml of absolutetetrahydrofuran are then added dropwise. When the addition has ended,the mixture is stirred at room temperature for 2 days, the solid whichhas precipitated is filtered off, the filtrate is concentrated in vacuo,the residue is dissolved in 300 ml of methylene chloride, the solutionis washed several times with a total of 200 ml of water and dried oversodium sulphate and the solvent is removed in vacuo. 62 g (86% oftheory) of 2-[1-(4-chlorophenoxy)-2-methylprop-2-yl]-1-methyl-oxiraneare obtained as an oil, which can be used in the next stage withoutfurther purification.

The following compounds of the formula (Ic) in which Y in the formula(I) represents the methylene group were obtained in a correspondingmanner and in accordance with the general preparation instructions:

    __________________________________________________________________________     ##STR144##                           (Ic)                                     Example No.                                                                          ##STR145##                                                                                    ##STR146##                                                                             Physical constant                            __________________________________________________________________________    (I-55)                                                                                ##STR147##                                                                                    ##STR148##                                                                            n.sub.D.sup.20 = 1.5059 (cis form)            (I-56)                                                                                ##STR149##                                                                                    ##STR150##                                                                            n.sub.D.sup.20 = 1.5114                       (I-57)                                                                                ##STR151##                                                                                    ##STR152##                                                                            n.sub.D.sup.20 = 1.5389 (cis form)            (I-58)                                                                                ##STR153##                                                                                    ##STR154##                                                                            n.sub.D.sup.20 = 1.5374                       (I-59)                                                                                ##STR155##                                                                                    ##STR156##                                                                            n.sub.D.sup.20 = 1.5129 (cis                  __________________________________________________________________________                                    form)                                     

The following compounds of the formula (Id) in which Y in formula (I)represents oxygen are also obtained in a corresponding manner: ##TBL6####STR157##

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A fungicidal composition comprising 1 to 50 parts by theweight of the compound of the formula ##STR158## and 1 part by weight ofthe compound of the formula ##STR159##
 2. A fungicidal compositioncomprising 50 parts by weight of the compound of the formula ##STR160##and 1 part by weight of the compound of the formula ##STR161##
 3. Amethod of combating fungi which comprises administration to such fungior to a fungus habitat a fungicidally effective amount of a compositionaccording to claim
 1. 4. A method of combating fungi which comprisesadministration to such fungi or to a fungus habitat a fungicidallyeffective amount of a composition according to claim 2.